Process for dyeing cellulose fibers



Dec. 15, 1953 J. WEGMANN ETAL 2,662,807 PROCESS FOR DYEING CELLULOSE FIBERS WITH DIRECT-DYEING CUPRIFEROUS AZO-DYESTUFFS AND DYEBATHS USED THEREFOR Filed Nov. 7, 1951 a z a mmvrons Jacques we m ann amp Karl Merv-l PW|; ATTORNEY Patented Dec. 15, 1953 PROCESS FOR DYEING CELLULOSE FIBERS WITH DIRECT-DYEING CUPRIFEROUS AZO-DYESTUFFS AND DYEBATHS USED THEREFOR Jacques Wegmann and Karl Menzi, Basel, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a Swiss firm Application November 7, 1951, Serial No. 255,247

Claims priority, application France November 10, 1950 17 Claims.

This invention is based on the observation that cellulose fibers can be dyed in a very advantageous manner with direct dyeing cupriferous or nickeliferous azo-dyestuffs, if a dyebath is used which contains an aliphatic amine having at least two nitrogen atoms each bound to two carbon atoms and at least two hydroxyl groups.

As cellulose fibers there come into consideration for example, cotton or linen, and also fibers of regenerated cellulose such as artificial silk 01' staple fibers, and furthermore mixtures of fibers containing cellulose fibers.

As direct dyeing cupriferous or nickeliferous azo dyestuffs there are to be understood complex copper or nickel compounds ofazo-dyestufis which possess an adequate aflinity for cellulose fibers and sufiicient solubility, and which can therefore be applied in dyeing by the known direct dyeing processes.

Among the aliphatic amines defined above there may be mentioned, for example, those of the general formula As examples may be mentioned the bases of the following composition:

HOOHz--CH2NHCH2 HO-OH2OHz-NHOH2 M. P. 93 to 94 C.

M. P. 136 to 139 C.

CH3 CH3 HO-QHrC-NH-CH:

no-om-o-mn- H:

C s CH3 M. P. 177 to 181 C. Especially suitable among, compounds of this stuffs. They may contain, for example, besides the dyestuif, sodium sulfate and/or sodium carbonate. The liquor ratio, that is to say the ratio of the quantity of the material to be dyed to the quantity of the dye liquor is in the present process variable within especially widelimits.

The addition of the amines of the above kind to the dyebaths influences the dyeing process and the results in an unexpected manner. The amine has a strong restraining action such that only a part of the dyestufi is taken up by the fiber and the remainder, which but for the addition of amine would have been taken up, remains in solution in the dyebath. This state of equilibrium is generally reached very rapidly at any given temperature with the result that further quantities of dyestufi cannot be taken up by prolonging the period of dyeing. The extent of the restraining action of the amine is different with different dyestuffs; in other respects it is dependent on the concentration, that is to say, on the content of amine in the dyebath. Even at very kind is the already mentioned 1:2-di-(13-hydroxyethylamino) -ethane of the formula HO-CHz-CH2-HN-CH2-CH2-NH-CH2-CH2-OH Apart from the content of an amine of the above kind, the dyebaths used in the present process high dilutions, for example, with 0.1 gram of amine per liter of dyebath, a very strong action is obtained in some cases. At a concentration of 3 grams of amine'per liter the maximum possible restraining action is usually obtained.

At any given amine concentration, quantity of dyestufi and quantity of material to be dyed the restraining action is constant within wide limits, that is to say, it is independent of the liquor ratio (it will be apparent from the foregoing that the amine concentration means the number of parts of amine present in 1000 parts by volume of dye liquor; that the quantity of dyestuff and the quantity of the material to be dyed mean the number of parts of these components; and that the liquor ratio means the ratio of the number of parts of the material to be dyed to the number of partsby volume of the dye liquor). Accordingly there are produced with dyebaths which are concentrated or dilute with respect to the dyestufi content therein, and which contain the same quantity of dyestuff and the same concentration of amine and, if salts such as sodium sulfate are present, the same concentration of salt, dyeings of practically the same strength on the same quantity of dyed goods.

By the addition of aldehydes, especially formaldehyde, the restraining action of the amine can be reduced, should this be desired.

The present invention constitutes a valuable advance in the art. Inter alia, it enables dyeing with direct dyeing cupriferous dyestuffs to be carried out in a specially advantageous manner.

When, for example, it is desired to dye a large quantity of textile material of the same tint and several dyeing operations are necessary for this purpose, this can be achieved by the present process in an especially simple and controllable manner. For this purpose the dyebath is made up by incorporating therein, on the one hand, a quantity of dyestufi many times, for example, times, the quantity necessary for producing the desired tint and, on the other, such a quantity of amine that only that proportion of the dyestuff present, for example, 1 6 thereof, which yields the desired strength of dyeing is taken up by the fiber. With respect to most dyestuffs the restraining action of the amine is so great that the dyestuff consumed in the first dyeing operation need not be replaced immediately or replaced with great accuracy. In general, when the dyestuff consumed in the first operation is not replaced, the second and in many cases further dyeings are so little weaker than the first dyeing that the differences in strength are not perceptible even to the eye of an expert. Accordingly, in some cases there are produced from the same dyebath without the addition of further dyestuff in two or more operations practically identical tints. It will also be apparent that even in cases where (after one or more dyeing operations) it is necessary to add fresh dyestufl for the subsequent dyeing operations, the quantity of the dyestufi to be added can be chosen freely within certain limits or made to suit prospective further needs, without there being any noteworthy deviation from the desired tint in the further dyeing operations. Likewise, if it is found in the course of a dyeing operation that the material already in the dyebath is not attaining the desired dyeing strength, it is easy to add fresh dyestuff while the goods are in the dyebath. Thus, there is no need to fear that the dyeing will be too strong nor is there any danger that the material will be non-uniformly dyed. The restraining action of the amine itself establishes the necessary equilibrium.

Owing to the fact that in the dyeing process of this invention the final dyeing strength is rapidly attained, the separate dyeing operations are completed in a, substantially shorter period than has been possible hitherto in direct dyeing rocesses. Moreover, it. is no longer necessary, in order to produce level dyeings, to introduce the goods into the dyebath at a low temperature and then to slowly raise the bath to he boil while moving the goods. The goods may be entered at 90 C. or a hi her temperature. It is.

no longer necessary to move energetically either the material tobe dyed or the dyeingliquor, and in spite of; this level dyeings. are obtained even with closely packed materials.

Dyeings on cellulose materials, which hfilve been produced with cupr ierous direct dyestufis by the rocesses hitherto known in the absence of an amine of the above kind, and which are faulty, for example, are too strong or are unlevel, can in some cases be very easily rectified by the present process, evenin the same dyebath and without loss of dyestuflf. By the addition to the dyebath of an amine having the constitution mentioned above, the greater part of the dyestuff can be removed from the fiber. When the dyeing is too strong, the excess or dyestufi can be removed by withdrawing a corresponding quantity of the dye liquor, which may, if desired, be replaced by water. Then advantageously after the dyebath has been cooled to some extent, the action of the amine can be reduced by an addition of formaldehyde and 4 dyeing is repeated in the same bath with the dyestuff that is at present in solution.

The following examples illustrate the invention, the parts and percentages being by weight unless otherwise stated and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the liter. The dyestufls used in these examples are in the ordinary commercial form, which have been brought to a predetermined standard strength by the addition of a salt.

Example 1 A dyebath is prepared from 6000 parts of water, 3 parts of the copper compound of the dyestufl obtained by coupling 2 molecular proportions of diazotized 2-amino-1-hydroxybenzene-4-sulfonic acid amide with 1 molecular proportion of 5:5- dihydroxy-2 :2'-dinaphthylamine-7 7-disulfonlc acid, the copper compound containing 2 atoms of copper bound in complex union per molecule of dyestufi, 30 parts of crystalline sodium sulfate and 6 parts of 1:2-di-(p-hydroxyethylaminolethane. parts of wetted cotton are entered into the dyebath at the boiling temperature, and boiling is continued for A hour. There are then added in several portions 6 parts by volume of formaldehyde solution of 30 per cent strength, and dyein is continued at the boil for a further 45 minutes. In this manner there is obtained a very well through-dyed and level violet dyeing. The dyeing is of the same strength as a dyeing produced by the usual methods with 3 parts of the, aforesaid cupriferous dyestuif.

By omitting the formaldehyde addition in the above dyeing procedure, there is. obtained after about 5 minutes a dyeing of which the strength corresponds to that of a dyeing obtained by the usual methods with 0.4 part of the dyestufi (0.4 per cent. dyeing) without the addition of the amine. By boiling for a longer time the dyeing is not strengthened. After removing from the dyebath the 100 parts of cotton so dyed, it is possible to. dye successively in the same bath without any further addition of dyestutf three further portions of 100 parts of cotton within a period of 15 minutes for each dyeing operation, practically the same dyeing strength (0.4 per cent) being obtained in each case. If after these four dyeing operations in the same bath, it is desired to produce further dyeings of the same strength a further 1 part 01 the dyestufi" must be added to the; dyebath in order to bring the ratio of the quantity ofdyestufi to. amine concentration to its original value.

The dyeing strength obtained in dyeing as described above without the addition of formaldehyde is dependent ontemperature to the extent that at a dyeing temperature of 20 C. a dyeing is obtained. of about double the strength of a dyeing obtained at the boiling temperature. From this it will be seen that a true equilibrium has been established, since a shifting of the equilibrium in favor of the dyestuff dissolved in the dyebath at a higher temperature is always possible, whereas the possibility of a longer time being required to establish the equilibrium at a high temperature than is required at a low temperature seems to be out of the question.

On the other hand the concentration of the dyestufl in the dyebath is variable within wide limits without affecting the strength of the dyeing produced. Thus, at a liquor ratio 01 1:20 practically the same dyeing strength is obtained as at a liquor ratio of 1:200.

5 6 The extent of the restraining action is dependsumed therefrom as to the actual distribution of ent on the concentration of amine in the dyeelectro and covalencies or as to the state of bath. If, instead of the above concentration of hydration of the complex compounds. 1 part of 1:Z-di-(p-hydroxyethylamino)-ethane For a given concentration of amine the in 1000 parts by volume of dye liquor, a concen- 5 strength of the resulting dyeing is approximately tration of 0.3 part in 1000 parts by volume is proportional to the dyestuff content of the dyeused there is obtained a 1 per cent. dyeing. With bath. Thus, if in this example, there is used, 1.6 parts of amine in 1000 parts by volume there instead of 3 parts, 8'parts of dyestufif, there is is obtained a 0.3 per cent. dyeing. Further obtained a 1 per cent. dyeing, with 16 partsof values, which illustrate how the dyeing strength 1 dyestuff there is obtained a 2 per cent. dyeing. depends on the concentration of amine for the Similar results are obtained when in the above above mentioned dyestuff (A) and three other processes the 1:2-di-(B-hydroxyethylamino)- dyestuffs (B, C and D), will be apparent from the ethane is replaced by one of the amines of the curves given in the accompanying drawing. In formulae I the drawing X=concentration of the 1 :Z-di-(e-hydroxyethyl- CH;

amino) -ethane, that is to say, the number of parts in 1000 parts by volume of dye liquor, Y=the strengths of the dyeing produced, ex-

pressed as percentages of the dyestufi used 20 H:

which in normal dyeing processes yield the same dye strengths as the' dyeings obtained and with the amine addition, that is to say the CH: om dyeing strengths which correspond to the dyeing strengths obtained in dyeing 100 parts of cotton with Y parts of dyestuffs without the addition of amine. CH3 CH3 A=the complex copper compound of the formula Example 2 O-Ou0 o-Ou 100 parts of cotton aredyed with 3 parts of the l I complex copper compound of the disazo dyestufi N=N from 2 molecular proportions of diazotized 2- 1 amino-1-hydroxybenzene-4-sulfonic acid and 1 HOaS- molecular proportion of 5:5'-dihydroxy-2:2-

ONH dinaphthyl-urea-7:7'-disulfonic acid by one of ONE? the usual methods for direct dyeing and in the the first Paragraphof this example) absence of an amine. By entering the cotton B =the complex copper compound of the formula which has thus been dyed a violet tint into a boiling bath which contains in 6000 parts of wac m ound o the formula C the complex Copper 0 p f ter 6 parts of 1:2-di-(fi-hydroxyethylamino) G0O--Cu0 OOu-0OO 5 ethane, and treating the material for about A hour at the boiling temperature, the dyestuff can 0 be practically completely removed. By the ad- HOKS JL SOH dition of formaldehyde the dyestuff removed can 56 be againtaken up by the fiber in the same dye- D=the complex copper compound of the formula bath. y

O--Cu0 o-'ou-o N=N N N 0 H035 NH&HN- soda H035 03H I (See Example 2) Example 3 In the above formulae the method of repre- 1 part of the nickel compound of the dyestufi senting the copper in complex union is one which of the formula v Hm o Nio 0-Ni--- NH; 1 we MPOQM as Hols m I is frequently used. However, nothing can be asis dissolved in parts of hot water.

2,002,807 7 8 10 parts oi this stock solution are added to hydroxyethylamino -ethane and the dyestufi of a dyebath consisting of 260 parts of water and the formula 30 parts of sodium sulfate solution of 10 per cent strength. Then 0.3 part of 1:2-di-(B-hydroxy- O Q ethylamino)-ethane are added.

parts of cotton are entered into the dye- N-N NH N N bath at the boiling temperature and a quar- Hogs sOaH ter 0! an hour later 3 parts oi. a formaldehyde solution of 3.3 per cent strength are gradually NE E NH added in the course of a quarter 0! an hour. 10

Dyeing is then continued for another 30 minutes 5. A process for dyeing cellulose fibers with diat the same temperature. The cotton is then rect-dyeing metalliferous azo dyestuffs which rinsed, centrifuged and dried. There is thus comprises using a dyebath containing lzz-di-(pobtained a reddish blue dyeing of outstanding hydroxyethylamino)-ethane and the dyestufl of levelness and penetration. the formula HOOC no 0Cu-0 What is claimed is: 6. A process for dyeing cellulose fibers with 1. A process for dyeing cellulose fibers with didirect-dyeing metalliferous azo dyestufis which rect-dyeing metalliferous azo dyestuffs containcomprises using a dyebath containing 1:2-di-(ping in complex union 2. metal having an atomic hydroxyethylamino)-ethane and the dyestuff of number ranging from 28 to 29 which process comthe formula prises using a dyebath containing an aliphatic 30 amine o! the formula. -O 0cu-ooo in which R1 indicates a member selected from the group consisting of a. hydrogen atom, an alkyl group with at most three carbon atoms and comprises using a dyebath containing 1:2-di-(pa. hydroxymethyl group, R2 indicates a member hydroxyethylamino)ethane and the dy stu 01 selected from the group consisting of a hydrogen the formula 7. A process for dyeing cellulose fibers with direct-dyeing metalliferous azo dyestuffs which KODL A0111 atom and a methyl group and n represents a 8. A process for dyeing cellulose fibers with diwhole number which is at most 4. rect-dyeing metalliferous azo dyestuiis which 2. A process for dyeing cellulose fibers with comprises using a dyebath containing 1:2-di-(fidirect-dyeing metalliferous azo dyestuffs conhydroxyethylamino) ethane and the dyestut! of taining in complex union a metal having an the formula 9. A dyebath which contains a direct-dyeing metalliferous azo dyestufi containing in complex di-(p-hydroxyethylamino) ethane. union 2. metal having an atomic number ranging 3. A process for dyeing cellulose fibers with from 28 to 29 and also contains an aliphatic direct-dyeing cupriferous azo dyestufis which amine of the formula comprises using a dyebath containing 1:2-di-(p- Rl hydroxyethylamino) ethane. l

4. A process for dyeing cellulose fibers with di- CH OH) rect-dyeing metalliterous azo dyestuffs which 1 comprises using a dyebath containing 1:2-di(fi in which R1 indicates a member selected from atomic number ranging from 28 to 29 which process comprises using a dyebath containing 1 :2-

the group consisting of a hydrogen atom, an alkyl 15. A dyebath which contains the metalliferous group with at most three carbon atoms and a azo dyestufi of the formula 0---0u0 OCu-O and also contains 1I2-di-(fi-hydroxyethylamino) ethane.

16. A dyebath which contains the metalliferous azo dyestuif of the formula HOaS hydroxymethyl group, R2 indicates a member selected from the group consisting of a hydrogen atom and a methyl group and n represents a whole number which is at most 4.

rm (I)--Ni-O O-Nl--O NH: HO..- N=N N=N 40...

H0: 03H 10. A dyebath which contains a direct-dyeing and also contains 1:2-cli-(fi-hydroxyethylamino)- metalliferous a-Zo dyestuif containing in complex union a metal having an atomic number ranging from 28 to 29 and also contains 1:2-di-(,8-hydroxyethylamino) -ethane.

11. A dyebath which contains a direct-dyeing cupriferous azo dyestuff and also contains 1:2-cli- (/i-hydroxyethyl-amino) -ethane. azc cly s ii f f ci t h gfifi i g the mebamfemus 30 with a direct-dyeing metalliferous azo dyestuff O-Ou-0 O-Cu0 containing in complex union a metal having an I I atomic number from 28 to 29 in a bath contain- N=N- NH- -N=N mg, 1n addition to the dyestuff on the fiber, an

H035 in aliphatic amine having at least 2 nitrogen atoms OZNH, OZNH, bound to 2 carbon atoms and having at least 2 and. also contains 1:2-di-(B-hydroxyethylamino) y yl roup ethane. 40

13. A dyebath which contains the metalliferous azo dyestuff of the formula OlH References Cited in the file of this patent UNITED STATES PATENTS ethane.

17. Process for the establishment of an equilibrium between the dyestufi in a dyebath and the dyestuff on the cellulose fibers in such bath,

comprising the treatment of cellulose fibers dyed JACQUES WEGMANN.

KARL MENZI.

and also contains 1:2-cli-(fl-hydroxyethylamino) ethane.

14. A dyebath which contains the metalliferous azo dyestufi of the formula Number Name Date COO. .Cu.. Q O -Cu- OOCE ,092,429 Straub Sept. 7, 1937 2,155,135 Kartaschoff Apr. 18, 1939 2,256,806 Kern Sept. 23, 1941 0 HO3S- NH- -HN 803E FOREIGN PATENTS Number Country Date and also contains 1:2-di-(p-hydroxyethylamino) 307,948 Great Britain Mar. 14, 1929 ethane. 

1. A PROCESS FOR DYEING CELLULOSE FIBERS WITH DIRECT-DYEING METALLIFEROUS AZO DYESTUFFS CONTAINING IN COMPLEX UNION A METAL HAVING AN ATOMIC NUMBER RANGING FROM 28 TO 29 WHICH PROCESS COMPRISES USING A DYEBATH CONTAINING AN ALIPHATIC AMINE OF THE FORMULA 